Fumigant compositions comprising 3-bromopropyne and 1, 2-dibromo-3-chloropropane



weight of United States Patent FUMIGANT COMPOSITIONS COMPRISING 3-BRO- MOPROPYNE AND 1,2-DIBROMO-3-CHLORO- PROPANE Chemical Company, Midland, Mich., a corporation of Delaware No Drawing. Application February .1, 19.57

1 SerialNor. 637,603

9 Claims. (CL' 167- 39) The present invention relates to'fumigant composi tions and is particularly concerned with a new fumigant composition and an agronomic'practice for improving the ability of soil to support plant growth.

It is an object of the present invention to provide a new fumigantcomposition. A 'further object is to supply anew agronomic practice for improving the'plant growing properties of soil'and the ability of soil to support the growth of crops. Another objectis the pro vision of a new method and composition for improving the emergence, seedling grow'thand the harvest of crop plants. A further object is the provision of "anew method and composition fortreating soilto obtain improved controls of soil-dwellinginvertebrate organisms such as wire worms and nematodes. An additional 'object is the provision of a new method and composition for treating soil which will "accomplish the stimulation of the growth of crops. 'Other objects w'ill become apparent from the following specification andclaims.

The new fumigant composition of the presentinven- 'tion comprises about 1 part'by weight of 3-bromopropyne in admixture with from about 0.1 to'9'partsby 1,2-dibromo 3-chloropropane. While "this composition advantageously may be employe'd inmany types of fumigation operations, it conveniently adapts itself to the treatment of soil or other growth media to improve the ability-of the soil to supportplant growth and to benefit the plants grown in the-treated soil. "Such practice protects the plants from'the ravages of'soildwelling invertebrate organisms which attack theiriroots and improves the growth an'dharvestof crop plants. '.It has also been found that the treatment accomplishes changes in the soil which stimulate thegrowthandirm prove the growth characteristics of cropsgrown .therein. It 'is among the advantages of the present invention that thetoxicants in the mixture appear .to be mutually activating so that .,a greater than additive or synergistic result isaccornplished .as regards the effect 'OI1' the {plant growing properties of the soil and the control of.i nsect and other .undesirable organisms and particularly invertebrates such as wire worms and nematodes.

The composition comprising the mixtureof toxicants is sufiiciently increased in effectiveness soas to permit the eifective utilization of reduced amounts of "3-br omopropyne and of 1,2-dibromor3-chloropropane and the obtaining of crop yields and controls of soil-dwelling organisms which are much superior to those obtained when either of the constituents of the mixture is employed alone. ,An additional advantage .isthat these -:materially reduce the hazards of soil residues.

2,849,361 Patented Aug. 26, 1$58 3-bromopropyne and 1,Z-dibromo-3-chloropropane are 7 mobile liquids which boil at 8890 C. and C. at atmospheric pressure, respectively. -Mixtures of the pompounds are somewhat soluble in many organic solvents and of low solubility in water and are adapted to bereadily and conveniently distributed in soil. It is among the advantages of the present invention that mixtures of these compounds, while sufliciently persistent to accomplish the desired eifect upon the soil and upon the soil inhabiting organisms, dissipate in a reasonable period of time. Still another advantage is that mixtures of these compounds permeate soil for a distance of several inches from the point of application depending upon the temperature, organic content, moisture content, compactness .and physical consistency of the soil or growth media.

'ln carrying out the improved agronomic practice of tithe invention, thei3-bromopropyne and 1,2-dibromo-3- "chloropropane may .be mixed together and such mix- .turesemployed .directly for the treatment of soil. However, the present invention also embraces the employmentof gaseous, liquid or dust-compositions containing -the mixture of toxicants and for any fumigant purpose where the composition is valuable. Thus,'-the mixture .Of 'toxicants may be dissolved in a suitable liquid carrier .to providecompositions adapted to be distributed in soil.

',.1ar or :finely divided solid carrier to providecomposi- :tions adapted to be distributed in soil or employed as .-concentrates and subsequently diluted with additional inert carrier to produce the ultimate treating compositions. In va further mode of operation, the 3-bromopropyneand 1,2-dibromo-3-chloropropanc may be blended with a suitable surface-active dispersing agent with or without one or more liquid carriers to' provide concentrates suitable for. dispersion in water to produce soil treatingcompositions in the form of dispersions or emulsions.

The compositions ofthe invention may-be prepared in anysuitablefashion. Since the-3-bromopropyne and :l,2-'dibrorno-3-chloropropane compounds are miscible'in all -proportions, compositions without carriers may be prepared by simple mixing ofthe components at ordisnarytemperatures. In-the preparation of compositions containing a liquid organic carrier, the-3-bromopropyne and 1,2 dibromo 3'- chloropropane components are -thoroughly mixed in the liquid organic carrier at ordinary temperatures. Suitable liquid organic carriers includeliquid aliphatic and aromatic hydrocarbons such as toluene, xylenes, naphthas and hydrocarbon mixtures derived from the distillation of petroleum or coal. For some fumigation operations, such carriers as carbon tetrachloride or ethylene dichloride may be employed. In general, it is preferred to, avoid liquid carriers having .such .-lowfla sh points as to constitute a, fire hazard or such high boiling points as to leave undesired residues after use of the compositions. Depending uponthe concentration of the mixture of toxicants, such augmented compositions are adapted to be distributed in the soil or otherwise employed as concentrates and subsequently diluted with additional carrier to produce the ultimate treating compositions.

In a preferred embodiment of the invention, selected petroleum distillates are employed as liquid carriers. Petroleum distillates used .in such embodiment are carefully fractionated portions boiling almost entirely under 400 F. at atmospheric pressure and having a flash point above about 80 F. These fumigant compositions are characterized by having excellent penetrating properties and by being of low fire hazard to the shipper and user.

In the preparation of dispersible concentrate compositions, the 3-bromopropyne and 1,2-dibromo-3-chloropropane components are mixed together in the proportions previously set forth together with a surface-active dispersing agent soluble in the composition with or without the further addition of a liquid organic carrier. The surface-active agents are usually employed in the amount of from 1 to 20 percent by weight of the combined weight of the toxicant mixture and surface-active agent. Suitable surface-active dispersing agents include polyoxyalkylene derivatives of alcohols, phenols and organic acids, oil-soluble petroleum sulfonates and polyoxyethylene derivatives of glycerol, glycols and the like.

In compositions in which the 3-bromopropyne and 1,2- dibromo-3-chloropropane components are dispersed on or in a granulated or finely divided solid carrier, said components may be added directly to the solid carrier with mechanical mixing. Alternatively, the components may be combined with one or more of the aforementioned liquid organic carriers and the resulting compositions admixed with the solid carrier. Suitable solid carriers include silica gel, wo'odfiour, fullers earth, chalk or gypsum and the like.

In formulating the compositions, it is essential to maintain the proportions of from about 1 part by weight of 3-bromopropyne to from 0.1 to 9 parts by weight of 1,2-dibromo-3-chloropropane and to provide an effective amount of said mixture in the finished composition in order to obtain the desired synergistic effect. The concentration of the mixture of toxicants in organic solvent compositions employed to supply the desired dosage is generally from about 10 to 85 percent by weight. With aqueous compositions, the required dosage is generally supplied with compositions containing from 1 to 50 percent, although concentrations of 0.0002 percent by weight conveniently may be employed in irrigation treatments of soil. In compositions wherein the active mixture is dispersed on the solid carrier, it is generally desirable to employ from about 1 to about 30 percent by weight of the above mixture of active ingredients in the finished solid composition. With high capacity carriers, such as silica gel, the active ingredients may amount to 50 percent by weight or more of the solid composition. In any case, it is desirable to employ suflicient or" the solid carrier so that the liquid composition is adsorbed or absorbed to provide a free-flowing solid mixture. In compositions to be employed as concentrates, the toxicant mixture oftentimes is present in a concentration of from about 5 to 95 percent by weight.

Alternatively, the liquid compositions may be injected into the soil at predetermined intervals. In any case, the active composition is usually deposited at a depth of from about 4 to 18 inches below the soil surface.

In row treatments it is advantageous to place the fumigant composition at least 12 inches below the surface of the seed bed and to seal in the fumigant by listing the soil or by other suitable means such as ring rollers or press sealers attached behind the applicator. In overall applications with chisel-type applicators, the fumigant composition may be applied in uniform treatments 1 to 12 inches apart at a depth of 6 to 8 inches. With plow sole applications, it is desirable to employ about 8 inches spacing between the furrows and to spray or otherwise introduce the fumigant composition so as to cover the bottom of the furrow. Where injection of the active composition at intervals is employed, good results are obtained when injecting at intervals of from 3 to about 12 inches, although somewhat greater intervals may be employed in certain cases. In the above operations, it is desirable to apply the fumigant composition after the soil has been worked into seed bed condition and when the soil temperature is above F. and the soil moisture content is sufficient for seed germination.

In another mode of operation, the fumigant composition in emulsifiable form may be dispersed in water employed to irrigate the soil. In this method, the amount of I S-chlbropropane composition to be employed will vary depending upon such factors as the type and condition of the soil, the varieties and growth stages of the pests to be controlled and the particular crop to be planted thereafter. The essential criterion is to employ an amount for accomplishing the desired effect upon the soil-dwelling invertebrate organisms and the plant growing properties of the soil. In general, good results are obtained when the mixture of toxi cants is distributed in growth media to a depth of from 4 to 12 inches and at a dosage of at The soil may be treated with a toxicant or a composition containing the mixture of toxicants in any suitable fashion. With liquid compositions, good results have been obtained by depositing the active fumigant mixture at regular intervals beneath the surface of the soil. Such deposition may be accomplished readily by automatic least one pound per acre. In field applications, the mixture of toxicants is usually introduced into the soil at a depth of about 6 inches and at a dosage of from 1 to 50 pounds per acre. Where compositions embodying a liquid or solid carrier are used, the amount of composition is adjusted to distribute substantially the above describedamounts of the active toxicant mixture per acre. ,The required amount of the toxicant mixture in the soil conveniently may be supplied per acre treated in from about 10 to gallons of organic solvent carrier, in from 10 to 162,000 gallons or more of the aqueous carrier or in from about 50 to 1,000 pounds or more of the solid carrier.

When operating in accordance wlth the present 1nvention, it isgenerally desirable to allow at least about 10d ay s after application of the active composition before planting the treated area to a crop. During such period, the fumigant mixture, after accomplishing its desired effects, is dissipated from the soil by processes such as leaching, volatilization and chemical degradation. If high dosages of the active composition are employed or if the temperature remains below about 60 C. or the soil is sealed by heavy rains or irrigation, av somewhat longer waiting period is desirable before planting. When employing high dosages or following periods of low temperature or high soil moisture, it is sometimes desirable to work the soil by harrowing or tilling several days before planting in order to facilitate the dissipation of the fumigant composition from the soil.

The following examples illustrate the invention but are not to be construed as limiting:

Example I 1,2 dibromo 3-chloropropane and 3-bromopropyne were dissolved in acetone to produce the followingcompositions:

These compositions were employed for the treatment of sandy loam soil heavily infested with root-knot nematodes. In such operations, the soil was placed in scalable containers and thereafter treated with the compositions by injection 'to give various dosages of toxicant per acre foot of soil. The containers of treated soil were then sealed and set aside for one week. Containers of untreated soil were similarly sealed and set aside to serve as checks.

Following the latter period, the containers were unsealed and the soil allowed to aerate for one Week and thereafter planted with tomato seeds. During the subsequent growing period, there was observed no adverse effect upon the growth of the seedlings attributable to the presence of residual toxicant. About 7 weeks after planting, the plants were lifted from the soil and the roots washed and examined for gall formation attributable to nematode attack. The results obtained together with the dosages at which the toxicants were employed are'set forth in the following table:

Dosage of toxicant in pounds per acre foot of soil Percent control Composition of nema- 1,2- todes dibromo- 3-bromo- 3-ch1oro- ,propyne propane A 0.2 B 1. 8 O O 0. 2 1. 8 100 In the check plots which received no treatment, the plants were found to be dwarfed and their roots heavily galled as a result of nematode attack.

Example 2 1,2-dibromo-3-ch1oropropane and 3-bromopropyne were dissolved in acetone to produce the following compositions:

These compositions were employed for the treatment of sandy loam soil heavily infested with root-knot nematodes. In such operations, the soil was placed in scalable containers and thereafter treated with the compositions by injection to give various dosages of toxicant per acre foot of soil. The containers of treated soil were then sealed and set aside for one week. Containers of untreated soil were similarly sealed and set aside to serve as checks.

Followingthe latterperiod, the containers were unsealed and the soil allowed to aerate for one week and thereafter planted with tomato seeds. During the subsequent growing period, .there was observed no adverse effect upon the growth of the seedlings attributable to the presence of residual toxicant. About 7 weeks after planting, the plants'were lifted from the soil and the roots washed and examined for gall formation attributable to nematode attack. The results obtained together with the dosages at which the toxicants were employed are set forth in the following table:

Dosage of toxicant in pounds per acre foot of soil Percent control Composition of nema- 1,2- todes dlbromo- 3-bromo- 3-ehloropropyne propane Example 3 l,2-dibromo-3-chloropropane and 3-bromopropyne were dissolved in acetone to produce the following compositions:

Amount of toxicant in grams per liter of acetone Composition 1 2. dibromo- 3-chloropropane B-bromo- D DY These compositions were employed for the treatment of sandy loam soil heavily infested with root-knot nematodes. In such operations, the soil was placed in sealable containers and thereafter treated with the compositionsby injection to give various dosages of toxicant per acre foot of soil. The containers of treated soil were then sealed and set aside for one week. Containers of untreated soil were similarly sealed and set aside to serve as checks.

Following the latter period, the containers were runsealed and the soil allowed to aerate for one week and thereafter planted with tomato seeds. During the subsequent growing period, there was observed no adverse efiect upon the growth of the seedlings attributable to the presence of residual toxicant. About 7 weeks after planting, the plants were lifted from the soil and the roots washed and examined for gall formation'attributable to nematode attack. The results obtained together with the dosages at which the toxicants were employed are set forth in the following table:

The roots of the tomato plants in the check plots which received no treatment were covered with galls resulting from nematode attack.

Example 4 1,2-dibromo-3-chloropropane and 3 bromopropyne were dissolved in acetone to produce the following compositions:

These compositions were employed for the treatment of sandy loam soil heavily infested with root-knot nematodes. In such operations, the soil was placed in sealable containers and thereafter treated with the compositions by injection to give various dosages of toxicant per acre foot of soil. The containers of treated soil were then sealed and set aside for one week. Containers of untreated soil were similarly sealed and set aside to serve as checks.

Following the latter period, the containers were unsealed and the soil allowed to aerate for one week and thereafter planted with tomato seeds. During the subsequent growing period, there was observed no adverse effect upon the growth of the seedlings attributable to the presence of residual toxicant. About 7 weeks after planting, the plants were lifted from the soil and the roots washed and examined for gall formation attributable to nematode attack. The results obtained together with the dosages at which the toxicants were employed are set forth in the following table:

Dosage of toxicant in pounds per acre foot of soil Percent control Composition of nema- 1,2- todes dlbromo- 3-bromo- 3-ch1oropropyne propane A 1. 45 B" 0.5 3 O 1. 5 0. 5 100 In the check plots which received no treatment, the plants were stunted and their roots heavily galled from nematode attack.

Example 5 Thirty parts by weight of 1,2-dibromo-3-chloropropane, 42 parts of 3-bromopropyne, 25 parts of xylene and 3 parts of a dimeric alkylated aryl polyether alcohol (Triton X-155) are mixed together to prepare a concentrate composition in the form of an emulsifiable liquid.

In a further operation, 33 parts by weight of 1,2-dibromo-3-chloropropane, 17 parts by weight of 3-bromo- In an additional operation, 1,2-dibromo-3-chloropropane and 3-bromopropyne are dissolved in Standard Thinner 250 to produce a fumigant composition containing 10 percent by weight of 1,2-dibromo-3-chloropropane and 15 percent by weight of 3-bromopropyne. Standard Thinner 250 is a petroleum hydrocarbon fraction boiling at from 192 to 272 F.

The concentrate compositions as above described are adapted to be dispersed in water to produce aqueous compositions having very desirable wetting and penetrating properties. The latter aqueous compositions and the above described fumigant compositions are adapted to be employed to treat soil and to distribute the mixture of toxicants therein in effective concentrations.

Example 6 1,2-dibromo-3-chloropropane and 3 bromopropyne were dissolved in acetone to produce the following compositions:

Amount of toxicant in grams per liter of acetone Composition 1 2 dlbrbmo- 3-ch1oropropane 3-br0mopropyne ers of untreated soil were similarly sealed and set aside to serve as checks.

Following the latter period, the containers were unsealedand the soil allowed to aerate for one week and thereafter planted with tomato seeds. During the subsequent growing period, there was observed no adverse effect upon the growth of the seedlings attributable to the presence of residual toxicant. About 7 weeks after planting, the plants were lifted from the soil and the roots washed and examined for gall formation attributable to nematode attack. The results obtained together with the dosages at which the toxicants were employed are set forth in the following table:

Dosage of toxicant in pounds per acre foot of soil Percent control Composition of nema- 1,2- todes dlbromo- 3-bromo- B-chloropropyne propane A 1.8 67 B 0.2 0 C 1.8 0.2

In the check plots which received no treatment, the plants were dwarfed and the roots covered with galls attributable to nematode attack.

Example 7 The water-dispersible concentrate composition described in Example 5 as prepared with Nacconal NR is dispersed in water to produce a composition containing 25 pounds of the mixture of toxicants per 200 gallons of ultimate mixture. This composition, while under agitation, is metered into irrigation water at the pump outlet at the rate of 2 gallons per 1,000 gallons of irrigation water. The water is in a state of turbulent flow as it comes from the pump which provides for the thorough mixing of the toxicants therein. About two acre inches of irrigation water is applied per acre to land heavily infested with wire worms and root-knot nematodes to accomplish a wetting of the soil to a depth of about six inches. Two weeks after the treatment, the soil is planted with tomatoes. In a check operation, adjacent but similarly infested soil is also planted with tomatoes. Eight weeks after seeding, the plots are inspected and representative plants lifted from the soil and the roots examined for evidence of wire worm and nematode attack. The examination indicates a commercial control of both soil organisms in the treated soil with severe infestation in the check plots.

We claim:

1. A fumigant composition comprising as active toxic ingredients from about 1 part by weight of 3-bromopropyne and from about 0.1. to 9 parts by weight of 1,2- dibromo-3-chloropropane, the active toxic ingredients of said composition being mutually activating.

2. A fumigant composition comprising a carrier and dispersed therein as active toxic ingredients from about 1 part by weight of 3-bromopropyne and from about 0.1 to 9 parts by Weight of 1,2-dibromo-3-chloropropane, the active toxic ingredients of said composition being mutually activating.

3. A composition comprising as active toxic ingredients from about 1 part by Weight of 3-bromopropyne and from about 0.1 to 9 parts by weight of 1,2-dibromo-3- chloropropane in intimate admixture with an adjuvant selected from the group consisting of (A) finely divided inert solids, (B) emulsifying and dispersing agents, and (C) petroleum distillates, the amount of such adjuvants employed in the compositions being from 70 to 99 percent by weight for (A), from 1 to 20 percent by weight for (B), and from 15 to 90 percent by weight for (C).

4. A composition claimed in claim 3 wherein the active toxic ingredients are admixed with a finely divided inert solid.

5. A composition claimed in claim 3 wherein the active toxic ingredients are admixed with a petroleum distillate.

6. A composition claimed in claim 3 wherein the active toxic ingredients are admixed with a surface-active dispersing agent.

7. A fumigant composition which comprises an aqueous dispersion of the composition claimed in claim 6, the mixture of active toxic ingredients being present in the amount of at least 0.0002 percent by weight.

8. in the practice of agricultural economy, the method which comprises impregnating soil with a parasticidal dosage of a composition comprising from about 1 part by weight of 3-bromopropyne and from about 0.1 to 9 parts by weight of 1,2-dibromo-3-chloropropane.

9. In the practice of agricultural economy, the method which comprises impregnating soil with a parasiticidal dosage of a composition comprising as active toxic ingredients from about 1 part by weight of 3-bromopropync and from about 0.1 to 9 parts by weight of l,2-dibromo- 3-chloropropane in intimate admixture with a petroleum distillate.

References Cited in the file of this patent UNITED STATES PATENTS 2,749,377 Johnston June 5, 1956 FOREIGN PATENTS 124,387 Australia June 12, 1947 913,365 France Sept. 5, 1946 OTHER REFERENCES Chem. Abstn, vol. 47 (1953), p. 488a. Ichikawa et al., Phytopathology, vol. 45, No. 10,

October 1955, p. 576.

Agri. Chem., February 1956, page 61.

Wadley, The Evidence Required to Show Synergistic Action of Insecticides and a Short Cut in Analysis, U. S. Dept. of Agri., Publication ET-233, June 1945. 

1. A FUMIGANT COMPOSITION COMPRISING AS ACTIVE TOXIC INGREDIENTS FROM ABOUT 1 PART BY WEIGHT OF 3-BROMOPROPYNE AND FROM ABOUT 0.1 TO 9 PARTS BY WEIGHT OF 1,2DIBROMO-3-CHLOROPROPANE, THE ACTIVE TOXIC INGREDIENTS OF SAID COMPOSITION BEING MUTUALLY ACTIVATING. 